Sure, but the comparable Rust feature is enum, not union.
That is essentially the motivation, primarily in the context of FFI where matching C's union behaviour using transmute is tricky and error-prone.
Also you can manually tag them and get s.th. more like other high level languages. It will just look ugly.
If you want disjoint types, something like Pascal's discriminated variants or Rust's enums is the way to go. It's embarrassing that C never had this.
Many bad design decision in C come from the fact that originally, separate compilation was really dumb, so the compiler would fit in small machines.
ColdString is easier to explain, the whole trick here is the "Maybe this isn't a pointer?" trick, ColdString might be a single raw pointer onto your heap with the rest of the data structure at the far end of the pointer, this case is expensive because nothing about the text lives inline, but... the other case is that your entire text was hidden in the pointer, on modern hardware that's 8 bytes of text, at no overhead, awesome.
CompactString is more like a drop-in replacement, it's much bigger, the same size as String, so 24 bytes on modern hardware, but that's all SSO, so text like "This will all fit nicely" fits inline, yet the out-of-line case has the usual affordances such as capacity and length in the data structure. This isn't doing the "Maybe this isn't a pointer?" trick but is instead relying on knowing that the last byte of a UTF-8 string can't have certain values by definition.
All ColdStrings which look like 8 bytes of UTF-8 text really are 8 bytes of UTF-8 text, just the type label on those 8 bytes isn't "[u8; 8]" an array of 8 bytes but instead "mut *u8" a raw pointer. "Validate" for example is 8 bytes of ASCII, thus UTF-8, and Rust is OK with us just saying we want a pointer on a 64-bit machine with those bytes. It's not a valid pointer, but it is a pointer and Rust is OK with that, we just need to be careful never to [unsafely] dereference the pointer because it's invalid
OK, so there are two cases left: First, what if there are fewer bytes of text? Zero even?
Since there are fewer than 8 bytes of text we can use the whole first byte to signal how many of the remainder are text, we use the UTF-8 over-long prefix indicator in which the top five bits of the byte are all set, bytes 0xF8 through 0xFF for this, there are eight of these bytes corresponding to our 8 lengths 0 through 7 inclusive. Because it's over-long this indicator isn't itself a valid UTF-8 prefix. Again we can pretend this is a pointer while knowing it's invalid.
Lastly, the seemingly trickiest problem, what if the string didn't fit inline? We use a heap allocation to store the text prefixed by a variable size integer length and we insist this allocation is aligned to 4 bytes. This means a valid pointer to our allocation has zeroes for the bottom two bits, then we rotate that pointer so those bottom two bits are at the top of the first byte position (depending on machine word layout) and we set the top bit. This is now always invalid UTF-8 because it has the continuation marker - the top bit is set but the next is not, which cannot happen in the first byte of any UTF-8 text, and so our code can detect this and reverse the transformation to get back a valid pointer using the strict provenance APIs if this marker is present.
This type is tomtomwombat's idea, credit to them:
As for C, it is a sharp blade on its own.
I can't even think of any prominent C FFI problems where I'd reach for the union's C representation. Too many languages can't handle that so it seems less useful at an FFI edge.
One of the reasons .NET had Managed C++, replaced by C++/CLI (nowadays C++20 compliant, minus modules), is exactly that P/Invoke (and RCW/CCW) cannot represent everything.
Which they don't want to expose on .NET type system directly.
I've seen exactly one Rust type which is actually a union, and it's a pretty good justification for the existence of this feature, but one isn't really enough. That type is MaybeUninit<T> which is a union of a T and the empty tuple. Very, very, clever and valuable, but I didn't run into any similarly good uses outside that.